JP3639684B2 - Evanescent wave detection microprobe and method for manufacturing the same, probe including the microprobe and method for manufacturing the same, evanescent wave detection device including the microprobe, near-field scanning optical microscope, and information reproducing device - Google Patents

Evanescent wave detection microprobe and method for manufacturing the same, probe including the microprobe and method for manufacturing the same, evanescent wave detection device including the microprobe, near-field scanning optical microscope, and information reproducing device Download PDF

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JP3639684B2
JP3639684B2 JP01582397A JP1582397A JP3639684B2 JP 3639684 B2 JP3639684 B2 JP 3639684B2 JP 01582397 A JP01582397 A JP 01582397A JP 1582397 A JP1582397 A JP 1582397A JP 3639684 B2 JP3639684 B2 JP 3639684B2
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microprobe
substrate
photoconductive material
layer
manufacturing
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JPH10197542A (en
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隆行 八木
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キヤノン株式会社
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/02Multiple-type SPM, i.e. involving more than one SPM techniques
    • G01Q60/06SNOM [Scanning Near-field Optical Microscopy] combined with AFM [Atomic Force Microscopy]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/18SNOM [Scanning Near-Field Optical Microscopy] or apparatus therefor, e.g. SNOM probes
    • G01Q60/22Probes, their manufacture, or their related instrumentation, e.g. holders
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q80/00Applications, other than SPM, of scanning-probe techniques
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00Nanotechnology
    • Y10S977/84Manufacture, treatment, or detection of nanostructure
    • Y10S977/849Manufacture, treatment, or detection of nanostructure with scanning probe
    • Y10S977/86Scanning probe structure
    • Y10S977/868Scanning probe structure with optical means

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a microprobe for detecting an evanescent wave used in a near-field scanning optical microscope, a manufacturing method thereof, a probe comprising a thin-film cantilever provided with the microprobe, a manufacturing method thereof, and an evanescent equipped with the microprobe. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wave detection device, a near-field scanning optical microscope, or an information reproduction device. About.
[0002]
[Prior art]
Recently, a scanning tunneling microscope (hereinafter referred to as “STM”) capable of directly observing the electronic structure of surface atoms of a conductor has been developed (G. Binig et al. Phys. Rev. Lett., 49, 57 (1983)). Scanning probe microscopes (hereinafter referred to as “SPM”) have been actively researched in the field of microstructure evaluation of materials since it has become possible to measure with high resolution of real space images regardless of single crystal or amorphous. It has come to be.
As the SPM, a scanning tunnel microscope (STM) that detects a surface structure using a tunnel current, an atomic force, a magnetic force, light, or the like obtained by bringing a probe having a microprobe close to a sample to be evaluated, There are an atomic force microscope (AFM), a magnetic force microscope (MFM), a near-field scanning optical microscope (NSOM), and the like.
[0003]
Among these SPMs, NSOM uses the evanescent light emitted from a minute pinhole to obtain a position resolution of λ / 2 or less, which has been impossible with conventional optical microscopes. Non-destructive measurement with high resolution. In NSOM, materials that have been difficult to observe conventionally, such as living organisms and cells, can be used as samples, and there are many objects that can be observed, and the application range is wide.
[0004]
[Problems to be solved by the invention]
There are the following three methods for detecting an evanescent wave.
In the first method, for example, illumination light is made incident from the back surface of the sample so as to satisfy the total reflection condition on the sample surface, and an evanescent wave generated on the sample surface by irradiation of the illumination light is used as a probe having a minute aperture. (E. Betzig, et al., “Collection mode near-field scanning optical microscopy”, Appl. Phys. Lett. 51 (25), 1987, pp 2088-2090). By this method, an image of a high resolution evanescent wave can be obtained, and most studies have been made.
However, a sharpened glass pipette or optical fiber is used as the probe, and it is manufactured by mechanical polishing or the like, so that productivity is low and manufacturing cost is high. Furthermore, it has been difficult to produce the aperture diameter with high reproducibility and high accuracy.
[0005]
The second method is a method of detecting scattered light of an evanescent wave using a thin film cantilever with a probe made of a silicon nitride film used for AFM without using an aperture (NF van Hulst, et. al., “Near-field optical microscopic using a silicon-nitride probe”, Appl. Phys. Lett. 62 (5), 1993, pp 461-463).
As a microprobe used in the above method and a manufacturing method thereof, a microprobe formed by anisotropic etching using single crystal silicon using a semiconductor manufacturing process technique is known (US Pat. No. 5,221,415). Specification).
As shown in FIG. 8, first, a pit 518 is formed on a silicon wafer 514 covered with a mask of silicon dioxide 510, 512 by anisotropic etching, and this pit is formed into a female probe. Then, the silicon dioxide 510 and 512 are removed, and then the silicon nitride layers 520 and 521 are coated on the entire surface to form a cantilever and a pyramidal pit 522 serving as a microprobe, and patterned into a cantilever shape. After that, the silicon nitride layer 521 on the back surface is removed, the glass plate 530 provided with the saw cut 534 and the Cr layer 532 is bonded to the silicon nitride layer 520, and the silicon wafer 514 is removed by etching to remove the nitride transferred to the mounting block 540. A probe made of silicon, consisting of a probe and a cantilever. (When used in an optical lever AFM, finally, a metal film 542 serving as a reflective film is formed on the back surface.) The probe of this method has a sharp tip shape, and has high productivity and production reproducibility.
However, the resolution of the second method is lower than that of the NSOM image measured by the probe with an aperture according to the first method.
[0006]
In the third method, the above two methods use a probe as a light pickup and detect the light by a photo detector of a photomultiplier tube arranged on the top of the probe, whereas a photodiode on a thin film cantilever is used. (S. Akamine, et al., “Development of a microphoton for near-field of the world's 150-year-of-the-world” FIG. 9 shows a sectional view of the probe.
The probe includes a p-layer 601 silicon thin film cantilever supported on one side by a silicon substrate 600, a pn junction 603 photodiode formed by forming an n layer 602 at the tip of the thin film cantilever, It consists of an Al metal wiring 605 provided on a silicon dioxide film 604 for extracting a scattered light signal detected by the photodiode.
The etch stop layer 606 used in manufacturing the cantilever is on the lower surface of the thin film cantilever.
By providing the photodetection portion of the photodiode at the free end of the cantilever, the photodetection portion and the sample can be brought close to each other, and the SN ratio can be improved, thereby improving the resolution. In addition, the system configuration can be simplified.
However, as shown in FIG. 9, the tip of the third method uses the tip of a thin film cantilever as the tip of the tip.
Since the thin film cantilever is manufactured by a photolithography process and etching, the probe shape is less reproducible than the second probe, and it is difficult to obtain a tip having the same shape between the manufactured lots.
[0007]
Accordingly, the present invention solves the above-described problems of the prior art, improves the S / N ratio by a microprobe that constitutes a light detection unit, and can exhibit excellent resolution and can detect an evanescent wave. And a manufacturing method thereof, and a probe including the microprobe and a manufacturing method thereof, and an evanescent wave detecting device, a near-field scanning optical microscope, and information capable of simplifying a system configuration by the microprobe The object is to provide a playback device.
The present invention also provides a microprobe for evanescent wave detection, a method for manufacturing the microprobe, capable of obtaining a uniform shape with good reproducibility as a microprobe, and capable of forming a sharp tip, and the microprobe. An object of the present invention is to provide a probe provided and a manufacturing method thereof.
Further, the present invention is a reusable female die for manufacturing a microprobe, a microprobe for detecting an evanescent wave capable of improving productivity and reducing manufacturing cost, and a manufacturing method thereof, Another object of the present invention is to provide a probe in which the microprobe is provided on a thin film cantilever and a manufacturing method thereof.
[0008]
[Means for Solving the Problems]
The present invention relates to a microprobe for detecting an evanescent wave and a manufacturing method thereof, a probe including the microprobe and a manufacturing method thereof, an evanescent wave detecting device including the microprobe, a near-field scanning optical microscope, The information reproducing apparatus is configured as follows.
That is, the microprobe of the present invention is a microprobe for detecting evanescent waves formed on a substrate, the microprobe is made of a photoconductive material, and the bottom of the microprobe is formed on the substrate. Was For applying voltage when detecting photocurrent It is characterized by being connected to an electrode.
The microprobe manufacturing method of the present invention is a method for manufacturing an evanescent wave detecting microprobe, and is a photoconductive material layer made of a photoconductive material on a release layer of a first substrate which is one substrate. And forming a microprobe by transferring the photoconductive material layer on the release layer onto the bonding layer made of the electrode material formed on the second substrate which is the other substrate. . And the manufacturing method is
(A) forming a recess in the surface of the first substrate;
(B) forming a release layer on the substrate including the concave portion of the first substrate;
(C) coating a photoconductive material layer made of a photoconductive material on a release layer including a recess in the first substrate;
(D) forming a bonding layer on the second substrate;
(E) bonding a photoconductive material layer on a release layer including a recess in the first substrate to a bonding layer made of an electrode material on the second substrate;
(F) at least a step of performing peeling at the interface between the release layer and the photoconductive material layer, or the interface between the release layer and the first substrate, and transferring the photoconductive material layer onto the bonding layer of the second substrate. It is characterized by.
In the microprobe and the manufacturing method thereof according to the present invention, the photoconductive material is made of an amorphous semiconductor material, and the amorphous semiconductor material is made of an amorphous silicon material or an amorphous chalcogenide material. It is a feature.
In addition, the microprobe and the manufacturing method thereof according to the present invention are characterized in that the photoconductive material is made of an organic photoconductor material.
The microprobe according to the present invention is characterized in that the microprobe has a pyramid shape and has a gap between the microprobe.
In the microprobe manufacturing method of the present invention, the first substrate is a single crystal silicon substrate, and a concave portion is formed on the substrate surface by crystal axis anisotropic etching.
In the method for manufacturing a microprobe of the present invention, the bonding layer is a metal.
The probe of the present invention is a probe having a microprobe for detecting evanescent waves, and the bottom of the microprobe made of a photoconductive material is attached to the free end of a thin film cantilever whose one end is fixed to the substrate. Formed on thin film cantilever For applying voltage when detecting photocurrent It is connected through an electrode.
The probe of the present invention is characterized in that the electrode is a bonding layer made of a metal for bonding a microprobe.
Further, the probe manufacturing method of the present invention is a probe manufacturing method comprising a microprobe for detecting evanescent waves and a thin film cantilever,
(A) forming a recess in the surface of the first substrate;
(B) forming a release layer on the substrate including the recess of the first substrate; and (c) coating a photoconductive material layer made of a photoconductive material on the release layer including the recess in the first substrate. And a process of
(D) forming a thin film cantilever on the second substrate;
(E) forming a bonding layer on the tip of the thin film cantilever;
(F) bonding a photoconductive material layer on a release layer including a recess in the first substrate onto a bonding layer made of an electrode material on the tip of the thin film cantilever;
(G) performing peeling at the interface between the release layer and the photoconductive material layer, or the release layer and the first substrate, and transferring the photoconductive material layer onto the bonding layer at the tip of the thin film cantilever;
(H) at least a step of removing a part of the second substrate under the thin film cantilever so that one end of the thin film cantilever is fixed to the second substrate.
The present invention also uses the above-described microprobe for detecting evanescent waves according to the present invention, and includes an evanescent wave provided with a voltage applying means for applying a voltage to the microprobe and a current detecting means for detecting a photocurrent. An evanescent wave generated in the sample by the light irradiating means is converted into a photocurrent by the microprobe and the voltage applying means, detected by the current detecting means, and optical information on the sample surface The evanescent wave generated on the recording medium by the light irradiation means is converted into a photocurrent by the microprobe and the voltage application means, detected by the current detection means, It is characterized in that an information reproducing apparatus for reproducing as recorded information by a processing circuit is configured.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, as described above, the microprobe is formed of a photoconductive material, so that the microprobe can be configured as a light detection unit, thereby improving the SN ratio and achieving excellent resolution. Is possible.
Moreover, since the microprobe can be formed by transferring the photoconductive material layer formed on the release layer on the first substrate to the bonding layer on the second substrate, the first substrate is removed by etching in a subsequent process. Without this, it is possible to form the micro-probe portion very easily and accurately in the joining and transferring process, and improve the productivity.
Furthermore, by forming a photoconductive material layer or a release layer and a photoconductive material layer after the transfer step, the first substrate that becomes a female mold can be used repeatedly, so that the manufacturing cost can be reduced. By using the same female mold, the shape reproducibility of the microprobe can be maintained.
Here, preferably, the first substrate is a single crystal silicon substrate, and a recess made of a (111) crystal plane is formed by anisotropic etching with a crystal axis.
By forming a microprobe material on a single crystal substrate on which a recess has been formed by crystal axis anisotropic etching, the recess that becomes the female die of the microprobe has a sharp tip, and when multiple tips are formed on the same substrate Have a uniform shape, and the resulting microprobe has a uniform characteristic.
Further, by using silicon for the first substrate, the concave surface can be thermally oxidized to form a silicon dioxide film (SiO2), and the radius of curvature at the tip of the probe can be made smaller.
This utilizes the fact that a difference occurs in the thickness of the silicon dioxide film when thermally oxidized due to the shape of the silicon. By controlling the thickness of the thermally oxidized silicon dioxide film, the radius of curvature of the probe is controlled. Is possible.
[0010]
As the peeling layer, it is necessary to select a photoconductive material layer or a material that is easily peeled from the first substrate.
That is, the material of the release layer needs to have low reactivity and adhesion with the photoconductive material or the first substrate.
As such a material, a suitable material may be selected depending on the combination with the photoconductive material or the first substrate, and various materials such as a metal, a semiconductor, and an insulator are selected. For example, when an amorphous inorganic semiconductor is used as a photoconductive material and peeling is performed between the release layer and the photoconductive material layer, the release layer is preferably a noble metal having low reactivity and adhesion, and Pt and an alloy material thereof are used. It is possible to use.
In the case where silicon is used as the first substrate and peeling is performed between the first substrate and the peeling layer, Ag can be used as the peeling layer.
However, Ag has a high light reflectivity, and evanescent waves cannot enter the photoconductive material layer through the Ag release layer. Therefore, the release layer on the photoconductive material layer is removed after the release layer is released from the first substrate. There is a need.
Since the release layer is formed in the recess on the first substrate, the release layer is formed using a thin film formation method so that the shape of the recess does not change significantly depending on the thickness of the release layer. As a thin film forming method, a vacuum evaporation method such as a resistance heating evaporation method, an electron beam evaporation method, a CVD method, or a sputtering method with high film thickness reproducibility may be used.
[0011]
A photoconductive material is a material that can absorb incident light and generate charges in the film without using a pn barrier or a depletion layer. A voltage is applied to both ends of the photoconductive material by a voltage applying means, and the charge is converted into a current. It can be taken out as a photocurrent by the detection means.
In other words, the present invention utilizes the photoconductive property of the photoconductive material, and the photoconductive material layer absorbs the evanescent wave generated on the sample surface scattered by the probe and applies a voltage to the photoconductive material layer. Is converted into a photocurrent and detected.
The photoconductive material is preferably a material that can be manufactured by a thin film manufacturing technique because it is formed in a fine recess provided on the first substrate. Amorphous inorganic semiconductors such as amorphous silicon and amorphous chalcogenide are preferable because they can be manufactured at a low temperature and the manufacturing method is easy. In addition, the organic photoconductor material is preferable because it is superior in mass productivity, cost, and safety as compared with the amorphous inorganic semiconductor.
[0012]
The bonding layer is formed on a substrate or a thin film cantilever, but is preferably made of a metal material so that an electrode provided for taking out a photocurrent can be used as the bonding layer, thereby simplifying the manufacturing process. it can.
The bond between the photoconductive material layer and the bonding layer is preferably a direct bond between the photoconductive material layer and the bonding layer. For example, when amorphous silicon is used as the photoconductive material layer, the bonding layer is silicided. It is selected depending on the material that can be formed.
When using a material that is difficult to react with a metal, such as an organic material, as the photoconductive material layer, a metal layer capable of metal bonding with the bonding layer is formed on the surface of the photoconductive material layer in contact with the bonding layer. Thus, the photoconductive material layer and the bonding layer can be bonded via the metal layer.
As a method for forming the bonding layer and the photocurrent extraction electrode, a conventionally known technique such as a vacuum deposition method, a sputtering method, a chemical vapor deposition method, a plating method, a thin film coating method or the like is used. Patterning into a desired shape is performed by applying a lithography process and etching.
[0013]
In the present invention, a layer to be a thin film cantilever is formed in advance on the second substrate, a patterned bonding layer is provided on the tip of the thin film cantilever, and the photoconductive material layer on the release layer is bonded to the bonding layer. After the transfer, a part of the second substrate under the thin film cantilever is removed so that one end of the thin film cantilever is fixed to the second substrate, thereby producing a cantilever type probe having a microprobe at the free end. It is possible.
The microprobe faithfully reproduces the surface shape of the recess formed on the first substrate, and a void is formed between the photoconductive material and the bonding layer. Thereby, when providing a microprobe at the free end of a thin film cantilever or the like, the weight is reduced, and a decrease in the resonance frequency of the cantilever with the probe can be suppressed.
[0014]
【Example】
Embodiments of the present invention will be described below with reference to the drawings.
[Example 1]
FIG. 1 (a) is a perspective view of an evanescent wave detection device comprising a microprobe of the present invention, and FIG. 1 (b) is a near-field scanning optical microscope using the same.
As shown in the figure, the microprobe is composed of a photoconductive material layer having a pyramid shape surrounded by four surfaces.
The evanescent wave detection device of the present invention includes a second substrate 12, a microprobe 20 made of a photoconductive material, electrodes 10 and 11 formed at both ends of the microprobe, and a voltage across the electrode 10 and the electrode 11. And a current detector 15 for converting the evanescent wave absorbed by the microprobe into a photocurrent and detecting the photocurrent.
A near-field scanning optical microscope using the evanescent wave detection device shown in FIG. 1B is a light source that enters a prism 153 as a sample stage and a sample 144 attached to the prism so that total reflection occurs from the back surface. NSOM laser beam 150, an XYZ-axis driving piezo element 145 as a driving means, an evanescent wave detection device that scans the sample on the XY plane by the XYZ-axis driving piezo element (FIG. 1A), and driving of the driving means It comprises an XYZ driving driver 157 for controlling and a signal processing circuit 155 for processing the signal of the current detector and displaying it on the display device 156.
In the near-field scanning optical microscope of the present invention, a photoelectric conversion device such as a photomultiplier conventionally required is not required, and the system configuration can be simplified.
[0015]
FIG. 2 is a cross-sectional view showing the steps of the microprobe manufacturing method according to the first embodiment of the present invention.
In FIG. 2A, a silicon wafer having a crystal orientation <100> on which a protective layer 2 made of a silicon dioxide film formed by thermal oxidation with an oxidizing gas is formed is prepared as the first substrate 1.
Using a photoresist formed by a photolithography process as a mask, a desired portion of the protective layer 2 was etched with an HF aqueous solution to expose 3 μm square silicon.
The protective layer 2 is a protective layer when the first substrate 1 is subjected to crystal axis anisotropic etching to form a concave portion that becomes a female tip of a microprobe, and has etching resistance to the crystal axis anisotropic etching solution. .
After the photoresist is peeled off, the first substrate is subjected to anisotropic crystal axis anisotropic etching with an aqueous solution of potassium hydroxide (KOH) having a concentration of 27% at a liquid temperature of 80 ° C. to form an inverted pyramid-shaped recess 3 made of a (111) crystal plane. Formed.
Next, the protective layer 2 is removed by etching with an aqueous HF solution, and then Ti and Pt are formed on the entire surface of the first substrate including the recesses 3 by sputtering using Ti and Pt targets, respectively, to form 50 nm and 700 mm respectively. Layer 4 was formed (FIG. 2B).
Next, as shown in FIG. 2C, a photoconductive thin film 5 was formed by depositing 1 μm of amorphous silicon as a microprobe material on the entire surface by plasma CVD (Chemical Vapor Deposition) using silane gas.
Next, a resist is applied, patterned by a photolithography process that exposes and develops, and the photoconductive thin film 5 is etched by reactive ion etching using CF4 gas using the photoresist as a mask to remove the photoresist. A patterned photoconductive material layer 7 was formed as shown in FIG.
[0016]
Next, Pyrex glass (trade name # 7059 Corning) is prepared as the second substrate 12, and Cr 50 Å and Au 1000 Å are successively deposited on the second substrate by an electron beam evaporation method, and the Cr and Au are photolithography-processed. Patterning was performed by a process and etching to form electrodes 10 and 11 (FIG. 2E).
Here, the electrode serves as a bonding layer for bonding the microprobe to the substrate. Subsequently, the photoconductive material layer 7 on the first substrate 1 and the electrodes 10 and 11 used as the bonding layers were aligned and contacted (FIG. 2 (f)).
Further, it was left for 1 hour at a temperature of 100 ° C. with contact. By applying pressure and pressure bonding while heating the first substrate and the second substrate, an alloy layer of Au and silicon is formed at the interface between the photoconductive material layer 7 and the electrodes 10 and 11, and silicide is formed and bonded. It peeled off from the interface of a peeling layer and a photoconductive material layer, and the microprobe 20 was formed (FIG.2 (g)).
Au has a higher reactivity with silicon than Pt, and can be peeled off at the interface between Pt and amorphous silicon when the first substrate and the second substrate are separated after contact. In the present invention, glass is used as the second substrate. This makes positioning at the time of joining extremely easy.
[0017]
When the fabricated microprobe 20 of the present invention was observed with an SEM (scanning electron microscope), the tip had a replicated shape reflecting the shape of an inverted pyramid formed by anisotropic etching of silicon crystal axis. It was confirmed that this was a microprobe having a sharp tip, and the tip curvature radius of the microprobe was 0.03 μm.
Further, the microprobe produced in this way has a gap between the second substrate.
With a near-field scanning optical microscope shown in FIG. 1B using the microprobe 20 of this example, a polycarbonate compact disk was used as the sample 144, and an NSOM image was observed.
As the NSOM laser beam 150, a HeNe laser was used. With this apparatus, it was possible to observe the pits and the grating of the compact disc, and it was possible to obtain a good NSOM image with good reproducibility. The resolution at that time was 40 nm or less.
[0018]
[Example 2]
Example 2 of the manufacturing method of the microprobe of the present invention is shown below.
FIG. 3 is a cross-sectional view showing the steps of a method for manufacturing a microprobe made of Se, which is chalcogenide glass.
The step of forming the recess in the first substrate was produced using the same method as in FIG.
As the first substrate, a silicon wafer having a crystal orientation plane of <100> on which a protective layer made of a silicon dioxide film formed by thermal oxidation with an oxidizing gas is formed is prepared as the first substrate 21.
Using a photoresist formed by a photolithography process as a mask, desired portions of the silicon dioxide film were etched with an HF aqueous solution to expose 3 μm square silicon.
After the photoresist is peeled off, the first substrate is subjected to crystal axis anisotropic etching with an aqueous solution of potassium hydroxide (KOH) having a concentration of 27% at a liquid temperature of 80 ° C. Formed. Next, after the silicon dioxide film was removed by etching with an HF aqueous solution, 700 mm of Ag was formed on the entire surface of the first substrate 21 including the recesses 23 by resistance heating vapor deposition to form a release layer 24 (FIG. 3A). ).
[0019]
Next, as shown in FIG. 3B, 1 μm of chalcogenide glass Se, which serves as a light-receiving portion of the evanescent wave, is formed by resistance heating vapor deposition to form a photoconductive thin film 25. Subsequently, Cr50% and Au1000% are formed on this surface. A thin metal film 26 was formed by successively depositing a thin film by an electron beam evaporation method.
The metal thin film was newly introduced for bonding between Se and an Au electrode used as a bonding layer in a later process. When joining Se and Au electrodes, it is necessary to form an alloy at the interface. However, the temperature at which Se crystallizes is low, and if heat treatment is performed for joining, it crystallizes and the photoconductivity decreases. By introducing the metal layer, the Se and the electrode can be joined at a low temperature through the metal layer.
Next, a resist is coated, patterned by a photolithography process of exposing and developing, the metal thin film 25 is ion milled with Ar ions (Ion Milling) using the photoresist as a mask, the photoresist is removed, and the metal layer 28 is removed. Formed. Similarly, the photoconductive thin film 25 was patterned using a photolithographic process and ion milling to form a photoconductive material layer 27 (FIG. 3C).
The metal layer 28 was patterned in the vicinity of the concave end of the photoconductive material layer. FIG. 3C shows a schematic top view thereof.
Since the metal layer is electrically connected to the electrode in a later step, the voltage applied to the photoconductive material layer can be lowered by patterning in the vicinity of the tip of the recess, and the photoconductivity of the charge generated by absorbing the evanescent wave can be reduced. The moving distance in the material layer can be shortened and the detection speed can be improved.
Since the microprobe of the present invention has a gap that becomes a recess on the back surface, it is possible to dispose an electrode near the tip of the recess on the back surface.
[0020]
Next, a second substrate 32 having electrodes 30 and 31 similar to those shown in FIG. 2E is prepared, and the metal layer on the photoconductive material layer shown in FIG. (FIG. 3 (d)).
At the time of contact, pressure is applied from the back surfaces of the first substrate and the second substrate and pressure bonding is performed, whereby an Au—Au metal bond is formed and bonded at the interface between the metal layer and the electrode, and the first substrate and the second substrate are bonded. Is released from the interface between the Ag peeling layer 24 and the silicon first substrate, and the microprobe 40 composed of the photoconductive material layer and the metal layer having the peeling layer 24 shown in FIG. Transferred onto the electrode.
The electrodes 30 and 31 are connected to both ends of the lower part of the microprobe. Furthermore, only the release layer was ion milled with Ar ions to expose the photoconductive material layer (FIG. 3 (f)), thereby forming an evanescent wave detection microprobe having a gap 33. .
[0021]
When the microprobe produced by the above-described method was observed with an SEM (scanning electron microscope), it was confirmed that the microprobe was made of Se with a sharp tip, and the tip curvature of the microprobe was confirmed. The radius was 0.04 μm or less.
When the microprobe 40 of this example is attached to the near-field scanning optical microscope shown in FIG. 1B and the SNOM image of the compact disk is observed in the same manner as in Example 1, a good SNOM image can be obtained. It was.
Next, after the Ag peeling layer is formed again on the first substrate which is the female substrate after the peeling layer and the photoconductive material layer are transferred and peeled, the steps shown in FIGS. 3B to 3F are performed. Thus, a microprobe could be formed on another second substrate provided with electrodes.
The tip radius of curvature of the microprobe was 0.04 μm or less, which was the same as the tip radius of curvature of the microprobe formed before reuse.
Thereby, it turned out that the 1st board | substrate used as the female type | mold of a microprobe can be reused. It was also found that there was no variation in the radius of curvature of the tip of the microprobe between lots.
[0022]
[Example 3]
Example 3 of the manufacturing method of the microprobe of the present invention is shown below.
FIG. 4 is a cross-sectional view showing the steps of a method for manufacturing a microprobe made of copper phthalocyanine (hereinafter referred to as “CuPc”), which is an organic photoconductor material.
The step of forming the recess in the first substrate was produced using the same method as in FIG.
As the first substrate, a silicon wafer having a crystal orientation plane of <100> on which a protective layer 42 made of a silicon dioxide film formed by thermal oxidation with an oxidizing gas is formed is prepared as the first substrate 41.
Using the photoresist formed by the photolithography process as a mask, a desired portion of the protective layer 42 was etched with an HF aqueous solution to expose 3 μm square silicon. After the photoresist is peeled off, the first substrate is subjected to crystal axis anisotropic etching with an aqueous solution of potassium hydroxide (KOH) having a concentration of 27% at a liquid temperature of 80 ° C. Formed.
[0023]
Next, the protective layer 42 was removed by etching with an aqueous HF solution, and then a release layer 44 made of a silicon dioxide film of 5000 mm was formed on the silicon substrate including the recesses 43 by a thermal oxidation process using an oxidizing gas (FIG. 4B). .
By forming the silicon dioxide film by thermally oxidizing the surface including the concave portion of the first substrate, the radius of curvature of the tip of the female probe for forming the microprobe can be further reduced.
This utilizes the fact that a difference occurs in the thickness of the silicon dioxide film when thermally oxidized due to the shape of the silicon. By controlling the thickness of the thermally oxidized silicon dioxide film, the radius of curvature of the probe is controlled. Make it possible to do.
Next, as shown in FIG. 4 (c), CuPc serving as an evanescent wave light receiving portion is formed into a 1 μm film by resistance heating vapor deposition to form a photoconductive thin film 45, followed by vacuum vapor deposition of Cr50Å and Au1000Å on this surface. The metal thin film 46 was formed by successively depositing the thin film.
The metal thin film was introduced in the same manner as in Example 2 for bonding to the electrode in a later step.
Next, a resist is applied, and the resist is patterned by a photolithographic process in which exposure and development are performed. Using the photoresist as a mask, the metal thin film 45 is ion-milled (Ion Milling) with Ar ions into a pattern shape of the photoconductive material layer, Next, the photoconductive thin film was etched by reactive ion etching using oxygen gas to form a photoconductive material layer 47, and the photoresist on the metal thin film was removed.
Similarly, a metal thin film on the photoconductive material layer 47 was patterned by using a photolithography process and ion milling to form a metal layer 48 (FIG. 4D).
The metal layer 48 was patterned in the vicinity of the concave end of the photoconductive material layer as in Example 2.
As a result, the voltage applied to the photoconductive material layer can be lowered, and the moving distance of the charge generated by absorbing the evanescent wave in the photoconductive material layer can be shortened, thereby improving the detection speed.
[0024]
Next, a silicon wafer was prepared as the second substrate 52, and 50 and 1000 Å of Ti and Pt were formed on the substrate by sputtering using respective targets, and a photolithography process and Ar plasma ions were used. The electrodes 50 and 51 used as the bonding layer were formed by etching. The metal substrate 48 on the photoconductive material layer 47 and the electrodes 50 and 51 were brought into contact with the second substrate and the first substrate shown in FIG. 4D (FIG. 4E).
At the time of contact, pressure is applied from the back surfaces of the first substrate and the second substrate and pressure bonding is performed, whereby an Au-Pt metal bond is formed and bonded at the interface between the metal layer and the electrode, and the first substrate and the second substrate are bonded. Is released from the interface between the silicon dioxide release layer 44 and the photoconductive material layer 47, and the microprobe 60 composed of the photoconductive material layer and the metal layer shown in FIG. The microprobe for detecting the evanescent wave having the gap 53 can be formed.
The electrodes 50 and 51 are connected to both ends of the lower part of the microprobe.
When the microprobe produced by the above-described method was observed with an SEM (scanning electron microscope), it was confirmed that the microprobe was made of CuPc with a sharp tip, and the tip curvature of the microprobe was confirmed. The radius was 0.03 μm or less.
When the microprobe 40 of this embodiment is attached to the near-field scanning optical microscope shown in FIG. 1 (b) and the NSOM image of the compact disk is observed in the same manner as the first embodiment, a good NSOM image is obtained. I was able to.
[0025]
[Example 4]
In the fourth embodiment, a method for manufacturing an evanescent wave detection probe in which a microprobe made of a photoconductive material layer made of amorphous silicon is provided on a thin film cantilever will be described.
A top view of the fabricated probe is shown in FIG. 5 (a), and a side view thereof is shown in FIG. 5 (b).
81 is a thin film cantilever, 70 and 71 are electrodes for taking out photocurrent used as a bonding layer, 80 is a microprobe made of a photoconductive material, 83 is a silicon dioxide film, and 82 is a silicon wafer etched from the back surface. A silicon nitride film 84 used as a mask is a silicon block for fixing and supporting one end of a thin film cantilever formed by etching a silicon wafer. The electrodes 70 and 71 are connected to both ends of the lower part of the microprobe.
[0026]
Hereinafter, the manufacturing process of the probe will be described with reference to FIG.
The process until the photoconductive material layer is formed on the release layer is manufactured by the same process as that shown in FIGS. 2A to 2D, and 1 μm of amorphous silicon serving as a microprobe is formed on the PtTi release layer. A photoconductive material layer was formed.
Next, a silicon wafer is prepared as the second substrate 72, a silicon dioxide film 83 is formed to have a thickness of 0.5 μm, and then the thin film cantilever 81 and the second substrate 72 are subjected to crystal axis anisotropic etching from the back surface in a subsequent process. A silicon nitride film serving as a mask was formed to a thickness of 0.5 μm by low pressure CVD (Low Pressure Chemical Vapor Deposition). The silicon nitride film on the upper surface of the second substrate was formed into a thin film cantilever shape shown in FIG. 5A by forming a photoresist cantilever pattern by a photolithography process and performing reactive ion etching using CF4.
Further, a part of the silicon nitride film 82 and the silicon dioxide film 83 on the back surface where the thin-film cantilever 81 of the second substrate is formed was patterned as shown in FIG. 5A by a photolithography process and reactive ion etching.
Next, Cr 50 Å and Au 1000 Å are sequentially deposited on the thin film cantilever 81 by electron beam evaporation, and the thin film is patterned by photolithography process and etching to form the electrodes 70 and 71 shown in FIG. (FIG. 6A).
Subsequently, the photoconductive material layer 67 on the release layer 64 of the first substrate 61 and the electrodes 70 and 71 on the second substrate 72 were aligned and joined (FIG. 6B). The bonding was performed by applying pressure to the back surfaces of the first substrate 61 and the second substrate 72 and pressing them, and left for 1 hour at a temperature of 100 ° C. while in contact.
As a result, bonding with Au is performed, the probe material layer 67 and the electrodes 71 and 71 are bonded, and the photoconductive material layer on the release layer is transferred onto the electrode by separating the first substrate and the second substrate after contact. As a result, the microprobe 80 was formed (FIG. 6C).
Next, silicon was etched from the back side of the second substrate by crystal axis anisotropic etching using an aqueous potassium hydroxide solution, and the silicon dioxide film was removed from the back side with an HF aqueous solution.
Thus, a probe having the microprobe 80 on the electrode at the free end of the thin film cantilever and one end of the thin film cantilever fixed to the silicon block 84 could be formed (FIG. 6D).
The evanescent wave detection probe produced by the manufacturing method of the present invention can be used as an AFM probe, and the reflection of the laser for displacement measurement is performed on the back surface of the electrode provided at the tip of the thin-film cantilever. Can be used as a substitute for a reflective film.
[0027]
A near-field scanning optical microscope capable of simultaneously observing the AFM image and NSOM image using the probe of this example was prepared. The AFM image is observed by an optical lever method.
A block diagram of this apparatus is shown in FIG. The near-field scanning optical microscope portion of this apparatus has substantially the same configuration as that shown in FIG. 1B, and is a light source that enters the prism 173 and the sample 164 attached to the prism so that total reflection occurs from the back surface. Laser beam 170, a voltage application circuit 169 that applies a voltage to electrodes 70 and 71 at both ends of the microprobe on the probe, a current detection circuit 168 that detects a photocurrent generated by the evanescent wave 171, and a probe It comprises an XYZ axis drive piezo element 165 to be scanned and an XYZ drive driver 167 for controlling the drive.
The probe for measuring the displacement of the thin film cantilever on the probe for AFM, the laser beam 161, the lens 162 for condensing the laser beam on the back surface of the bonding layer at the free end of the thin film cantilever, and the deflection of the thin film cantilever A position sensor 163 that detects a change in the reflection angle of light due to the displacement and a displacement detection circuit 166 that detects the displacement by a signal from the position sensor are attached.
The signal processing circuit 175 causes the display device 176 to display the AFM image and the NSOM image using the XYZ driving driver, the displacement detection circuit signal, and the current detection circuit 168 signal.
In the near-field scanning optical microscope of the present invention, a photoelectric conversion device such as a photomultiplier that has been conventionally required is not required, the system configuration can be simplified, and the region required for the photoelectric conversion device can be used for AFM image observation. The optical system and displacement detection circuit could be arranged. As the NSOM laser beam 170, a HeNe laser was used.
[0028]
Using this apparatus, the probe was brought close to the sample 164 made of a compact disc, and then the NSOM and AFM of the sample surface were simultaneously observed by driving the XY directions of the XYZ axis driving piezo elements.
As a result, the displacement of the probe was detected, and AFM images of pits and gratings were obtained. At the same time, a good NSOM image with a resolution of 40 nm or less could be obtained.
In addition, since the bits of the compact disc that is the sample can be detected, the detected bit data can be used as an information reproducing device by decoding it with the signal processing circuit instead of NSOM image data and reproducing it as recorded information. It was.
[0029]
【The invention's effect】
As described above, the present invention comprises a microprobe for detecting an evanescent wave with an improved S / N ratio and having an excellent resolution by forming a photodetection portion with a microprobe made of a photoconductive material, and a manufacturing method thereof, and A probe including the microprobe and a method for manufacturing the probe can be provided.
In addition, according to the method for manufacturing a microprobe of the present invention, a microprobe for detecting an evanescent wave, which has a reproducible and uniform shape as a microprobe and has excellent characteristics with a sharp tip, is manufactured. In addition, since the first substrate in which the concave portion is formed can be repeatedly used as the female die of the microprobe, the productivity can be improved and the manufacturing cost can be reduced.
Further, by using such a microprobe of the present invention, an evanescent wave detection device, a near-field scanning optical microscope, and an information reproducing device with a simplified system can be configured. In addition, a conventional photoelectric conversion device such as a photomultiplier is not required, and an optical system and a displacement detection circuit for observing an AFM image can be formed in a region where such a photoelectric conversion device is required. NSOM and AFM Simultaneous observation can be performed.
[Brief description of the drawings]
FIG. 1A is a perspective view for explaining an evanescent wave detection device of the present invention, and FIG. 1B is a block diagram for explaining a near-field scanning optical microscope of the present invention.
FIG. 2 is a cross-sectional view showing a manufacturing process of a microprobe manufacturing method in Embodiment 1 of the present invention.
FIG. 3 is a cross-sectional view showing a manufacturing process of a microprobe manufacturing method in Embodiment 2 of the present invention.
FIG. 4 is a cross-sectional view showing a manufacturing process of a microprobe manufacturing method in Example 3 of the present invention.
5A is a top view for explaining an evanescent wave detection probe of the present invention, and FIG. 5B is a side view.
FIG. 6 is a cross-sectional view showing a manufacturing process of a microprobe manufacturing method in Embodiment 4 of the present invention.
FIG. 7 is a block diagram illustrating a near-field scanning optical microscope composed of a microprobe according to Example 4 of the present invention.
FIG. 8 is a cross-sectional view showing the main steps of a conventional method for manufacturing a microprobe.
FIG. 9 is a cross-sectional view of a conventional microprobe.
[Explanation of symbols]
1, 21, 41, 61: first substrate
2, 42: protective layer
3, 23, 43: recess
4, 24, 44, 64: Release layer
5, 25, 45: Photoconductive thin film
7, 27, 47, 67: Photoconductive material layer
10, 11, 30, 31, 50, 51, 70, 71: Electrode
12, 32, 52, 72: second substrate
13, 33, 53, 73: gap
14: Power supply for bias application
15: Current detector
20, 40, 60, 80: microprobe
26, 46: Metal thin film
28, 48: Metal layer
81: Thin film cantilever
82: Silicon nitride film
83: Silicon dioxide film
84: Silicon block
144, 164: Sample
145, 165: XYZ axis drive piezo elements
150, 170: Laser beam for NSOM
151, 171: Evanescent wave
153, 173: Prism
155, 175: signal processing circuit
156, 176: Display device
157, 167: XYZ driver
161: Laser light
162: Lens
163: Position sensor
166: Displacement detection circuit
510, 512: Silicon dioxide
514: Silicon wafer
518: Pit
520, 521: silicon nitride layer
522: Pyramid pit
530: Glass plate
532: Cr layer
534: Saw cut
540: Mounting block
542: Metal film
543: Magnetic layer
600: Silicon Motosaka
601: p layer
602: n layer
603: pn junction
604: Silicon dioxide film
605: Metal wiring
606: Etch stop layer

Claims (18)

  1. A microprobe for detecting evanescent waves formed on a substrate, wherein the microprobe is made of a photoconductive material, and the bottom of the microprobe has a voltage when detecting a photocurrent formed on the substrate. A microprobe for detecting an evanescent wave, characterized by being connected to an electrode for application .
  2. The microprobe according to claim 1, wherein the photoconductive material is made of an amorphous semiconductor material.
  3. The microprobe according to claim 2, wherein the amorphous semiconductor material is made of an amorphous silicon material or an amorphous chalcogenide material.
  4. The microprobe according to claim 1, wherein the photoconductive material is made of an organic photoconductive material.
  5. The microprobe according to any one of claims 1 to 4, wherein the microprobe has a pyramid shape and has a gap between the microprobe.
  6. A method of manufacturing a microprobe for detecting evanescent waves, wherein a photoconductive material layer made of a photoconductive material is formed on a release layer of a first substrate that is one substrate, and a second substrate that is the other substrate is formed. A method of manufacturing a microprobe for detecting evanescent waves, wherein a microprobe is manufactured by transferring a photoconductive material layer on the release layer onto a bonding layer made of an electrode material formed on the substrate.
  7. The manufacturing method of the micro probe for detecting the evanescent wave is as follows.
    (A) forming a recess in the surface of the first substrate;
    (B) forming a release layer on the substrate including the concave portion of the first substrate;
    (C) coating a photoconductive material layer made of a photoconductive material on a release layer including a recess in the first substrate;
    (D) forming a bonding layer on the second substrate;
    (E) bonding a photoconductive material layer on a release layer including a recess in the first substrate to a bonding layer made of an electrode material on the second substrate;
    (F) peeling off the release layer and the photoconductive material layer or the interface between the release layer and the first substrate, and transferring the photoconductive material layer onto the bonding layer of the second substrate;
    The method for producing a microprobe according to claim 6, comprising: at least.
  8. 8. The method of manufacturing a microprobe according to claim 6, wherein the photoconductive material is made of an amorphous semiconductor material.
  9. 9. The method of manufacturing a microprobe according to claim 8, wherein the amorphous semiconductor material is made of an amorphous silicon material or an amorphous chalcogenide material.
  10. The method of manufacturing a microprobe according to claim 6 or 7, wherein the photoconductive material is made of an organic semiconductor material.
  11. 8. The method of manufacturing a microprobe according to claim 7, wherein the first substrate is a single crystal silicon substrate, and a recess is formed on the substrate surface by crystal axis anisotropic etching.
  12. The method for manufacturing a microprobe according to any one of claims 6 to 11, wherein the bonding layer is a metal.
  13. A probe having a fine tip for evanescent wave detection, to the free end of the thin-film cantilever having one end fixed to the substrate, light bottom of micro-probe consisting of photoconductive material, is formed on the thin film cantilever A probe for detecting evanescent waves, which is connected via an electrode for applying a voltage when detecting a current .
  14. The probe for detecting evanescent waves according to claim 13, wherein the electrode is a bonding layer made of a metal for bonding the microprobe.
  15. A method of manufacturing a probe comprising a microprobe for detecting evanescent waves and a thin film cantilever,
    (A) forming a recess in the surface of the first substrate;
    (B) forming a release layer on the substrate including the concave portion of the first substrate;
    (C) coating a photoconductive material layer made of a photoconductive material on a release layer including a recess in the first substrate;
    (D) forming a thin film cantilever on the second substrate;
    (E) forming a bonding layer on the tip of the thin film cantilever;
    (F) bonding a photoconductive material layer on a release layer including a recess in the first substrate onto a bonding layer made of an electrode material on the tip of the thin film cantilever;
    (G) performing peeling at the interface between the release layer and the photoconductive material layer, or the release layer and the first substrate, and transferring the photoconductive material layer onto the bonding layer at the tip of the thin film cantilever;
    (H) removing a part of the second substrate below the thin film cantilever so that one end of the thin film cantilever is fixed to the second substrate;
    A method for producing a probe, comprising:
  16. An evanescent wave detection device comprising a microprobe, a voltage applying means for applying a voltage to the microprobe, and a current detecting means for detecting a photocurrent, wherein the microprobe is claimed in claims 1 to 2. An evanescent wave detection device comprising the microprobe described in any one of 5 above.
  17. Microprobe, voltage application means for applying voltage to the microprobe, current detection means for detecting photocurrent, drive means for scanning the probe and its drive control means, and irradiating the sample with light It consists of a light irradiation means and a sample stage for holding a sample. The evanescent wave generated in the sample by the light irradiation means is converted into a photocurrent by the microprobe and the voltage application means and detected by the current detection means. A near-field scanning optical microscope for obtaining optical information on the sample surface, wherein the microprobe is constituted by the microprobe according to any one of claims 1 to 5. Near-field scanning optical microscope.
  18. A recording medium; a microprobe; a voltage applying means for applying a voltage to the microprobe; a current detecting means for detecting a photocurrent of the microprobe; The evanescent wave generated on the recording medium by the light irradiation means is converted into a photocurrent by the microprobe and the voltage application means, detected by the current detection means, and recorded information by the signal processing circuit. An information reproducing apparatus that reproduces the microprobe as described above, wherein the microprobe is constituted by the microprobe according to any one of claims 1 to 5.
JP01582397A 1997-01-13 1997-01-13 Evanescent wave detection microprobe and method for manufacturing the same, probe including the microprobe and method for manufacturing the same, evanescent wave detection device including the microprobe, near-field scanning optical microscope, and information reproducing device Expired - Fee Related JP3639684B2 (en)

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JP01582397A JP3639684B2 (en) 1997-01-13 1997-01-13 Evanescent wave detection microprobe and method for manufacturing the same, probe including the microprobe and method for manufacturing the same, evanescent wave detection device including the microprobe, near-field scanning optical microscope, and information reproducing device
US09/005,016 US6211532B1 (en) 1997-01-13 1998-01-09 Microprobe chip for detecting evanescent waves probe provided with the microprobe chip and evanescent wave detector, nearfield scanning optical microscope, and information regenerator provided with the microprobe chip
EP98100404A EP0853251B1 (en) 1997-01-13 1998-01-12 Microprobe chip for detecting evanescent waves and method for making the same, probe provided with the microprobe chip and method for making the same, and evanescent wave detector, nearfield scanning optical microscope, and information regenerator provided with the microprobe chip
DE69839658A DE69839658D1 (en) 1997-01-13 1998-01-12 Microprobe chip for detecting evanescent waves and method for its production, probe with this microprobe chip and its manufacturing method as well as evanescent wave probe, optical near field scanning microscope and Informationsregenerator with the microprobe chip

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JPH10197542A (en) 1998-07-31
US6211532B1 (en) 2001-04-03

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